1/20/2013

Chemistry Review

Abdel Fattah Hasan, Ph.D.

Civil Engineering Department
An-Najah National University

Environmental Engineering II

for use with

Water and Wastewater Engineering
By
Mackenzie L. Davis

pH

pH = - log [H+], [] in mol/L

Generally, pX = - log X

pOH = - log [OH-], [] in mol/L

H2O H++OH-

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Water yields one hydroxyl (basic) ion

for each hydrogen (acid) ion
Pure water is considered neutral
When an acid is added to water, pH
the hydrogen ion concentration
increases, resulting in a lower pH
number

Acid

Water yields one hydroxyl (basic) ion

for each hydrogen (acid) ion
Pure water is considered neutral
An alkaline substance lowers pH
the hydrogen ion
concentration, causing a
higher pH number

Alkaline

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Chemical Reactions

Chemical reactions can be classified

into:

1. Homogeneous reactions:
All reactants and products are in
the same physical state

2. Reactants and products are in

different same physical states

Equilibrium Constant (K)

Consider the general equilibrium
reaction:
aA + bB cC + dD

Equilibrium constant (K);

[ C ]c [ D ]d
K= [ A]a [ B ]b

pK=-log K

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Kw Ka Kb

H2O H++OH-

Kw = [H+] [OH-]

pKw=pH + pOH

Acid reactions: Ka

Base Reactions: Kb

Carbonate Buffer System

Example of Homogeneous reactions
Buffer Solution: is a solution that resists large
changes in pH when an acid or base is added or
when the solution is diluted is called a.
Atmospheric carbon dioxide (CO2) produces a
natural buffer through the following reactions:

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Behavior
of the
carbonate
buffer
system
with the
addition of
acids and
bases or
the
addition
and
removal of
CO2

CaCO3-water system
Example of Heterogeneous reactions

CaCO3(s) Ca2+(aq) + CO32-(aq)

Ksp = [Ca2+] [CO32-]

pKsp = -log Ksp

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ELEMENTS, RADICALS, AND COMPOUNDS

Fundamental chemical identities

that form all substances are
referred to as elements
 Each differs from any other in weight,
size, and
chemical properties
 Elements can appear in nature as
gases, liquids
or pure solids

Symbols for elements are used in
writing chemical formulas and
equations

ELEMENTS, RADICALS, AND COMPOUNDS

Information about elements common to

water and wastewater technology is given
in Table 2–1

Certain groupings of atoms—called

radicals—act together as a unit in a number
of different molecules (Table 2–2)

Radicals themselves are not compounds,

but join
with other elements to form compounds
(Table 2–3)

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Equivalent weight (EW)

Atomic / MolecularWeight ( GMW )

EquivalentWeight ( EW ) = Valency / Ch arg e ( n )

Concentrations - Review

M; mol/L

Mg/L

ppm

%

meq/L

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Example:

Convert the concentration of 667

mg/L Iron(II) Sulfate into meq/L.

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CHEMICAL WATER ANALYSIS

Laboratory tests on water

determine concentrations
of particular ions in solution. (Table
2–4)
 Normally expressed as weight of the
element or
radical in milligrams per liter of water

Graphical presentation of a water

analysis is performed by plotting
the values to scale
(Fig. 2–1)

CHEMICAL WATER ANALYSIS

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CHEMICAL WATER ANALYSIS

Alkalinity

In freshwaters, alkalinity is primarily due

to the presence of bicarbonate salts

Alkalinity is always measured in units of
equivalents/L or normality

Also can be measured as mg/l CaCO3

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Alkalinity
Often we would rather use molar
concentrations:
Total Alkalinity (in eq/L) =
[HCO3-] + 2[CO32-] + [OH-] - [H+]

Implicit in this is a conversion factor:

(1 equivalents/mol) for HCO3-, OH-, H+
(2 equivalents/mol) for CO32-
When using the units mg/L as CaCO3 the terms are
added directly. The multiple of two for CO32- has
already been accounted for in the conversion

Titration curve for a hydroxide-carbonate mixture

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Estimating Alkalinity

At pH values between 6 and 8

(H+) ≈ (OH-) → terms cancel
Then: Alkalinity (meq/L) ≈ (HCO3-) + (CO32-)

HCO3- ↔ H+ + CO32- Ka = 10-10.33

[H + ] [CO32- ]
= 10-10.33
[HCO-3 ]
[CO 32- ]
If pH < 8 then < 10 - 2.33
[HCO -3 ]

Alkalinity (meq/L) ≈ (HCO3-)

Note: this is true for pH between 6 and 8

Example 1
A water contains 100.0 mg/L CO32- and
75.0 mg/L HCO3- at a pH of 10.

a) Calculate the alkalinity exactly at 25 oC.

b) Approximate the alkalinity by ignoring

[OH-] and [H+].

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Hardness

A term often used to characterize the
ability of a water to:
 cause soap scum
Ca2+ + (Soap)- ↔ Ca(Soap)2 (s)
 increase the amount of soap needed
 cause scaling on pipes
 cause valves to stick due to the formation
of calcium carbonate crystals
 leave stains on plumbing fixtures

Hardness

Total Hardness
 Technically - the sum of all polyvalent
cations
 Practically - the amount of Ca and Mg ions
(the predominant minerals in natural
waters)
 It is divided into
 Carbonate hardness (CH)
 noncarbonate hardness (NCH)

Total Hardness (TH) = CH + NCH

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Hardness

Description Hardness range

(mg/L as CaCO3)
Extremely soft 0 - 50
Very soft 50 100
Moderately hard 100 – 150
Hard 150 - 300
Very hard > 300

Formation of Hardness

Precipitation

Topsoil

Subsoil

CO2 + H2O → H2CO3

Limestone CaCO3(s) + H2CO3 → Ca(HCO3)2

MgCO3(s) + H2CO3 → Mg(HCO3)2

GW

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Hardness

Carbonate Hardness
 Often called "temporary hardness" because
heating the water will remove it. When the
water is heated, the insoluble carbonates
will precipitate and tend to form bottom
deposits in water heaters.
 Ca2+, Mg2+ associated with HCO3-, CO32-
 CH = TH or Total alkalinity, whichever is
less

Hardness

Non-Carbonate Hardness
 Called permanent hardness because it is not
removed when the water is heated. It is
much more expensive to remove non-
carbonate hardness than carbonate
hardness.
 Ca2+, Mg2+ associated with other ions, Cl-,
NO3-, SO42-
 NCH = TH - CH
 If Alkalinity ≥ Total hardness, then NCH = 0

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Hardness Units

milligrams per liter (mg/L) as calcium

carbonate

parts per million (ppm) as calcium
carbonate

grains per gallon of hardness (to
convert from grains per gallon to mg/L,
multiply by 17.1)

equivalents/liter or meq/L

Example 1: Hardness

A sample of water having a pH of 7.2
has the following concentrations of ions
Ca2+ 40 mg/L
Mg2+ 10 mg/L
Na+ 11.8 mg/L
K+ 7.0 mg/L
HCO3- 110 mg/L
SO42- 67.2 mg/L
Cl- 11 mg/L

Calculate the TH, CH, NCH, Alkalinity,
and construct a bar chart of the
constituents

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Example 1: Hardness

Ion Conc. M.W. Eq. Wt. Conc. Conc.

n
mg/L mg/mmol mg/meq meq/L mg/L as
CaCO3
Ca2+ 40.0 40.1
Mg2+ 10.0 24.3
Na+ 11.8 23.0
K+ 7.0 39.1
HCO3- 110.0 61.0
SO42- 67.2 96.1
Cl- 11.0 35.5

Example 1: Hardness
Ion Conc. M.W. n Eq. Wt. Conc. Conc.
mg/L mg/mmol mg/meq meq/L mg/L as
CaCO3
2+
Ca 40.0 40.1 2 20.05
Mg2+ 10.0 24.3 2 12.15
Na+ 11.8 23.0 1 23.0
+
K 7.0 39.1 1 39.1
HCO3 110.0 61.0 1 61.0
-
2-
SO4 67.2 96.1 2 48.05
-
Cl 11.0 35.5 1 35.5

Sample Calc: Equivalent Weight of Ca2+ = M.W. / |n|

= 40.1/2
= 20.05

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Example 1: Hardness
Ion Conc. M.W. n Eq. Wt. Conc. Conc.
mg/L mg/mmol mg/meq meq/L mg/L as
CaCO3
2+
Ca 40.0 40.1 2 20.05 1.995
2+
Mg 10.0 24.3 2 12.15 0.823
+
Na 11.8 23.0 1 23.0 0.51
+
K 7.0 39.1 1 39.1 0.179
HCO3 110.0 61.0 1 61.0 1.80
-
2-
SO4 67.2 96.1 2 48.05 1.40
-
Cl 11.0 35.5 1 35.5 0.031
Sample Calculation: Concentration of Ca2+ =
(Concentration in mg/L) / (Equivalent Weight in
mg/meq) = (40.0 mg/L) / (20.05 mg/meq)
= 1.995 meq/L

Example 1: Hardness
Ion Conc. M.W. n Eq. Wt. Conc. Conc.
mg/L mg/mmol mg/meq meq/L mg/L as
CaCO3
2+
Ca 40.0 40.1 2 20.05 1.995 99.8
2+
Mg 10.0 24.3 2 12.15 .823 41.2
+
Na 11.8 23.0 1 23.0 .51 25.7
+
K 7.0 39.1 1 39.1 .179 8.95
HCO3 110.0 61.0 1 61.0 1.80 90.2
-
2-
SO4 67.2 96.1 2 48.05 1.40 69.9
Cl- 11.0 35.5 1 35.5 .031 15.5
Sample Calculation: Concentration of Ca2+ in mg/L as
CaCO3 = (Concentration in meq/L) * (Equivalent
Weight of CaCO3) =
(1.995 meq/L) X (50 mg/meq) = 99.8 mg/L as CaCO3

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Example 1: Hardness

Example 1: Hardness

Check Solution
Σ(cations) = Σ(anions) to within ± 10%
175.6 = 175.6 mg/L as CaCO3

(Can check using concentrations in meq/L or

mg/L as CaCO3)

Total Hardness = Σ of multivalent cations
= (Ca2+) + (Mg2+) =
99.8 + 41.2 =
141 mg/L as CaCO3

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Example 1: Hardness

Alkalinity = (HCO32-) + (CO32-) + (OH-) - (H+)
Since pH = 7.2 →
Alkalinity ≅ (HCO32-) = (1.80) meq/L
Alkalinity = (1.80 x meq/L)(50 mg/meq)
= 90.1 mg/L as CaCO3

Example 1: Hardness

Carbonate Hardness (the portion of the

hardness associated with carbonate or bicarbonate)
Alkalinity = 90.1 mg/L as CaCO3
TH = 141 mg/L as CaCO3
CH = 90.1 mg/L as CaCO3
(Note: if TH < Alk then CH = TH; and NCH = 0 )

Non-carbonate Hardness
NCH = TH - CH = 141 - 90.1 =
50.9 mg/L as CaCO3

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